Process for the preparation of lactams and sulfonic acid derivatives

ABSTRACT

A PROCESS FOR THE PREPARATION OF LACTAMS AND SULFONIC ACID DERIVATIVES OF ACTIVE HYDROGEN-CONTAINING ORGANIC COMPOUNDS OF THE GROUP CONSISTING OF OXIMES, ALCOHOLS, PHENOLS, THIOLS, PRIMARY AMINES AND SECONDARY AMINES, WHICH COMPRISES REACTING A LACTAM-O-SULFONIC ACID WITH A COMPOUND SELECTED FROM THE SPECIFIED ORGANIC COMPOUNDS UNDER SUBSTANTIALLY ANHYDROUS CONDITIONS.

United States Patent 3,836,525 PROCESS FOR THE PREPARATION OF LACTAMSAND SULFONIC ACID DERIVATIVES Mitsuo Masaki, Chiba, and Masaru Uchida,Taizi Oda, and Koichi Yamamoto, Ichihara, Japan, assignors to UbeIndustries, Ltd., Yamaguchi-ken, Japan No Drawing. Filed Sept. 15, 1970,Ser. No. 72,551 The portion of the term of the patent subsequent to Oct.24, 1989, has been disclaimed Int. Cl. C07d 41/06 US. Cl. 260-2393 A 3Claims ABSTRACT OF THE DISCLOSURE A process for the preparation oflactams and sulfonic acid derivatives of active hydrogen-containingorganic compounds of the group consisting of oximes, alcohols, phenols,thiols, primary amines and secondary amines, which comprises reacting alactam-O-sulfonic acid with a compound selected from the specifiedorganic compounds under substantially anhydrous conditions.

This invention relates to a process for the preparation of lactams andsulfonic acid derivatives. More particularly, the invention relates to aprocess comprising reacting lactim-O-sulfonic acids with activehydrogen-containing organic compounds, thereby producing correspondinglactams and the sulfonic acid derivatives of said organic compounds.

We discovered that when lactim-O-sulfonic acids are treated with activehydrogen-containing compounds selected from the group consisting ofoximes, alcohols, phenols, thiols, and primary and secondary amines, thecorresponding lactams and sulfonic acid derivatives of the organiccompounds are simultaneously obtained.

The lactim-O-sulfonic acids employed in this invention can berepresented by the general formula,

in which n is a number of 3 to 11, and each of R and R is hydrogen atom,an alkyl or alkenyl group.

Among such lactim-O-sulfonic acids, those of which R and R are bothhydrogen atoms are preferred for the purpose of this invention. Examplesof such acid include butyrolactim-O-sulfonic acid,valerolactim-O-sulfonic acid, caprolactim-O-sulfonic acid,enantholactim-O-sulfonic acid, caprylolactim-O-sulfonic acid,pelargonolactim-O- sulfonic acid, caprilactim-O-sulfonic acid,undecanolactim- O-sulfonic acid, and laurolactim-O-sulfonic acid.

Whereas, those lactim-O-sulfonic acids of the formula (I) in whicheither one or both of R and R are alkyl group, preferably alkyl groupsof up to 4 carbons such as methyl, ethyl, and propyl groups; or arealkenyl groups of preferably 2-4 carbons such as vinyl and allyl groups;are also useful for the invention. Examples of such acids include'y-methylcaprolactim-O-sulfonic acid, v-ethylcaprolactim-O-sulfonicacid, B-propylvalerolactim-O-sulfonic acid,'y-propylvalerolactim-O-sulfonic acid, 'y-vinylcaprolactim-O-sulfonicacid, 'y-allylcaprolactim-O-sulfonic acid, etc.

As the active hydrogen-containing organic compounds, any of oximes,alcohols, phenols, thiols, and primary and secondary amines can be usedin the invention. Upon reacting such an organic compound withlactim-O-sulfonic acid, the compound itself is sulfonated to become asulfonic acid derivative, While converting the lactim-O-sulfouic acid tothe corresponding lactam.

-As the oximes, alicyclic ketoximes of the formula in which n, R and Rhave the already defined significations, and acyclic ketoximes of theformula NOH in which each of R and R, is a monovalent hydrocarbonradical of up to 14 carbons, for example, alkyl group of up to 10carbons, cycloalkyl group of 3 to 12 carbons, aryl group of 6-14carbons, or aralkyl group of 7 to 14 carbons,

are conveniently used.

As the alicyclic ketoximes, those in which the R and R in the formula(II) are hydrogen atoms are particularly preferred, specific examplesincluding cyclobutanone oxime, cyclopentanone oxime, cyclohexanoneoxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime,cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime.

Whereas, those alicyclic ketoximes in which either one or both of R andR are alkyl groups of preferably up to 4 carbons, such as methyl, ethyl,and propyl groups; or alkenyl groups of preferably 2 to 4 carbons suchas vinyl and allyl groups, are also useful. Examples of such ketoximesinclude 4-methylcyclohexanone oxime, 4-ethylcyclohexanone oxime,3-propylcyclopentanone oxime, 4-vinylcyclohexanone oxime,4-allylcyclohexanone oxime, etc.

As the examples of acyclic oximes of the general formula (III),acetoxime, methyl ethyl ketoxime, cyclohexyl methyl ketoxime,acetophenone oxime, benzophenone oxime, benzyl methyl ketoxime, etc. maybe named.

The alcohols useful in the invention include:

(a) monohydric alcohols of the formula,

R OH (IV) in which R, is an alkyl group of up to 18 carbons, cycloalkylgroup of 4 to 12 carbons, or an aralkyl group of 7 to 14 carbons,

for example, methyl alcohol, ethyl alcohol, propyl alcohols, butylalcohols, amyl alcohols, octyl alcohol, dodecanol, myristyl alcohol,cetyl alcohol, stearyl alcohol, cyclohexanol, methyl cyclohexanol,benzyl alcohol, phenyl ethyl alcohol, cinnamyl alcohol, phenyl propanol,etc.

(b) glycols of the formula,

HOR (OR OH (V) (e) high molecular weight alcohols such as polyvinylalcohol.

The phenols useful for the invention are those of the formulae,

( ilk in which R, is hydroxyl, an alkyl group of up to 4 carbons,

or nitro group, and k is 0, l, or 2.

and

(VII) R SH (VIII) in which R is an alkyl group of up to 10 carbons,cycloalkyl group of 4 to 12 carbons, aralkyl group of 7 to 14 carbons,or an aryl group of 6 to 14 carbons,

are usable. Specific examples include methylmercaptan,

ethylmercaptan, hexylmercaptan, cyclohexylmercaptan,4-methylcyclohexylmercaptan, benzylmercaptan, and thiophenol.

As the primary and secondary amines, those of the formula,

are used. Specific examples include primary monoamines such asmethylamine, ethylamine, butylamine, cyclohexylamine, benzylamine,phenethylamine, aniline, anisidine, and naphthylamine; secondarymonoamines such as dimethylarnine, diethylamine, dibutylarnine,N-methylcyclohexylamine, N-methylbenzylamine, and N-benzylaniline;polyamines such as ethylenediamine, propylenediamine,hexamethylenediamine, phenylenediamine, xylylenediamine, andtriethylenetetrarnine; and cyclic: amines such as aziridine, azetidine,pyrrolidine, piperidine, and piperazine.

According to the invention, among those active hydrogen-containingorganic compounds, particularly those of the formula,

R YI-I (X) in which Y is oxygen or sulfur atom, or a group, NR

R being hydrogen atom or an alkyl group of up to 6 carbons, and R is amonovalent hydrocarbon radical of 1 to 18 carbons or an alkylideneiminogroup of the formula,

in which R R and n have the previously defined significations or of theformula,

(XII) in which R and R have the previously defined significations,

when R is an alkylideneimino group, Y being oxygen atom, are preferred.

The reaction of this invention can be illustrated, for example, by thereaction formula below:

(XIII) The reaction of lactim-O-sulfonic acids with activehydrogen-containing organic compounds is performed under substantiallyanhydrous conditions, preferably in inert, organic solvent. While roomtemperature is quite satisfactory, the reaction is normally performed attemperatures ranging from -30 C. to 50 C., the lower temperatures beingpreferred. As the inert, organic solvents, halogenated hydrocarbons suchas methylene chloride, ethylene chloride, chloroform and carbontetrachloride; ethers such as ethyl ether, isopropyl ether, dioxane, andtetrahydrofuran; and aromatic hydrocarbons such as benzene, toluene,xylene, and ethylbenzene; may be named. Obviously, solvents other thanabove-named may be employed, so far as they are inert, particularly tolactim-O sulfonic acids. The important factor in the reaction is thesufiiciently intimate contact of the lactirn-O-sulfonic acids with theactive hydrogen-containing organic compounds. When the reactants arewell contacted, the reaction proceeds quantitatively, with ease and at ahigh rate.

Through the reaction of lactim-O-sulfonic acids with activehydrogen-containing organic compounds, the corresponding lactams andsulfonic acid derivatives of the organic compounds are formed.

The lactams can be represented by the formula,

NH (XIV) in which R R and n have the already defined significations,

and correspond to the lactirn-O-sulfonic acids employed. As suchlactams, therefore, butyrolactam, valerolactam, caprolactam,enantholactam, caprylolactam, pelargonolactam, caprilactam,undecanolactam, laurolactarn, other alkyl lactams and vinyl lactams maybe named.

According to the invention, together With the above lactams, sulfonicacid derivatives of the employed active hydrogen-containing organiccompounds are obtained. For instance, when oximes are used,corresponding oxime- O-sulfonic acids are obtained. Thus, use ofalcohols produces alcohol-O-sulfonic acids; that of phenols, phenol-O-sulfonic acids; that of thiols, thiol-S-sulfonic acids; and that ofprimary or secondary amines, sulfamic acids.

For example, when the oximes of foregoing formulae (II) and (III) areused as the most significant embodiment of the invention,ketoxime-O-sulfonic acids of the formula,

R R (XVI) in which R R R R and n have the previously definedsignifications are obtained.

Those ketoxime-O-sulfonic acids represented by above general formulaeinclude, for example, acetoxime-O-sulfonic acid, methyl ethylketoxime-O-sulfonic acid, cyclohexyl methyl ketoxime-O-sulfonic acid,acetophenone oxime-O-sulfonic acid, benzophenone oxime-O-sulfonic acid,benzyl methyl ketoxime-O-sulfonic acid, cyclobutanone oxime-O-sulfonicacid, cyclopentanone oxime-O-sulfonic acid, cyclohexanoneoxime-O-sulfonic acid, cycloheptanone oxime-O-sulfonic acid,cyclooctanone oxime-O- sulfonic acid, cyclononanone oxime-O-sulfonicacid, cyclodecanone oxime-O-sulfonic acid, cycloundecanone oxime-O-acid,and cyclododecanone oxime-O-sulfonic acid.

The reaction products in this embodiment are normally obtained in theform dissolved in the solvent. Therefore, the separation of formedlactam from the ketoxime- O-sulfonic acid is efiected by adding a baseto the reaction mixture to precipitate the ketoxime-O-sulfonic acid as asalt with the base, and recovering the lactam from the mother liquor.

As the base useful for this purpose, oxides, hydroxides, carbonates orbicarbonates of alkali metals such as lithium, sodium, and potassium,and of alkaline earth metals such as magnesium, calcium, and barium,etc. may be named, but use of organic bases is more advantageous.

Useful organic bases include:

(1) aliphatic primary amines, such as methylamine, ethylamine,n-butylamine, isobutylamine, ethylenediamine, propylenediamine, andhexamethylenediamine;

(2) aliphatic secondary amines such as dimethylamine,

diethylamine, n-dibutylamine, and diisobutylamine; (3) aliphatictertiary amines such as trimethylamine, triethylamine, tripropylamine,n-tributylamine, and triamylamine;

(4) alicyclic amines such as cyclohexylamine, N-methylcyclohexylamine,and dicyclohexylamine;

(5) aromatic amines such as aniline, paranitroaniline,

anisidine, N-methylaniline, N,N-diethylaniline, naphthylamine, andN,N-di-n-butylaniline;

(6) nitrogen-containing heterocyclic compounds such as imidazole,pyridine, morpholin, and pyrimidine; and (7) amidines such asbenzylthioformamidine and acetoamidine.

The ketoxime-O-sulfonic acids in the reaction mixtures readily formsalts, when treated with equivalent quantity of the bases asabove-described.

The salts of organic bases with ketoxime-O-sulfonic acids have neverbeen disclosed in prior arts. Since they are stably present in manysolvents as precipitates, the above-described separation means is quitevaluable as an isolating method of the ketoxime-O-sulfonic acids.

Because the salts of organic bases with ketoxime-O- sulfonic acids formprecipitates in the named solvents in majority of cases, they can beeasily separated. When the salt is soluble in the solvent employed, thesalt can be collected by first removing the solvent and then extractingthe formed lactam with a solvent which dissolves the lactam alone.

In the reaction mixtures of the lactams and ketoxime-O- sulfonic acidsas obtained in the subject process, it is normally difiicult to causerearrangement of the ketoxime- O-sulfonic acids to lactim-O-sulfonicacids without additional processing. Whereas, when the halides which areLewis acids are caused to be present in the reaction mixtures, it isdiscovered that the ketoxime-O-sulfonic acids can be rearranged tolactim-O-sulfonic acid. In that case, the lactams in the reactionmixtures become complexes of the lactams with the halides.

As the halides which are Lewis acids, those of the general formula,

Mx (XVII) in which M is an element of Group IB of periodic table, suchas copper; Group IIB, such as zinc, Group IIIA, such as boron andaluminum; Group IVA, such as tin; Group IVB, such as zirconium; GroupVA, such as antimony; or Group VIII, such as nickel and iron;

X is a halogen atom such as fluorine, bromine and chlorine, and

p is a number equalling the valency of M,

are employed. Incidentally, the periodic table referred to herein isthat of Werner-Pfeifer. Preferred halides are, by the order of theirimportance, stannic chloride, stannic bromide, zirconium tetrachloride,zinc chloride, boron trifluoride, antimony pentachloride, borontrichloride, and aluminium trichloride.

The halide may be added to the reaction system after the completion ofreaction of the lactim-O-sulfonic acid with the ketoxime, or added inadvance of completion of said reaction. Preferably the quantity of saidhalide is at least stoichiometric to the finally formed quantity of thelactam.

This reaction can be illustrated by the reaction formula below,

(XVIII) in which R R n, M, X, and p have already defined significations,and a is /2 or 1.

The reaction is exothermic, and it proceeds at a suificlent rate at roomtemperature.

Thus in the presence of a halide which is a Lewis acid in the reactionmixture, the lactam forms a complex with the halide, while theketoxime-O-sulfonic acid is readily rearranged to lactim-O-sulfonic acidwhich can be successively used in the reaction with the ketoxime.

According to this embodiment of the invention, it becomes possible toadd a large excess of the ketoximes and the halides Which are Lewisacids, to the lactim-O-sulfonic acids present in the reaction system,either incrementally or continuously, recovering substantially all theketoximes as the complexes of the lactams with the halides.

Because the lactam-halide complexes exhibit less solubility in organicsolvents compared with the lactams, they can be recovered as solids fromthe reaction mixtures. Treating the complexes with bases of strongerbasicity than that of the lactams, for example, ammonia, free lactamscan be obtained.

When alcohols are used as the active hydrogen-containing organiccompound, the products corresponding to the employed alcohols areobtained. For example, methyl alcohol-O-sulfonic acid, ethylalcohol-O-sulfonic acid, propyl alcohol-O-sulfonic acid, butylalcohol-O-sulfonic acid, amyl alcohol-O-sulfonic acid, octylalco'hol-O-sulfonic acid, dodecanol-O-sulfonic acid, benzyl alcohol-O-sulfonic acid, cyclohexanol-O-sulfonic acid,methylcyelohexanol-O-sulfonic acid, ethylene glycol-0,0'-disulfonicacid, propylene glycol-0,0'-disulfonie acid, polyethyleneglycol-0,0-disulfonic acid, polypropylene glycol-0,0- disulfonic acid,1,3-butanediol-0,0'-disulfonic acid, 1,6- hexanediol-0,0'-disulfonicacid, as well as glycerin and polyvinyl alcohol in which the alcoholicresidue is sulfonated, are formed.

Similarly, when the phenols of formula (VI) or (VII) are used,phenol-O-sulfonic acids represented by the formulae;

in which R is a radical selected from the group consisting of hydroxylgroup, OSO H group, alkyl groups of up to 4 carbons, and nitro group,and

k has the already defined signification,

are formed. Likewise, with the thiols of formula (VIII),thiol-S-sulfonic acids of the formula,

R SSO H in which R has the already defined signfication,

(XXI) are formed, and with the amines of formula (IX), sulfamic acids ofthe formula,

in which R R 11 and l have the significations as already defined, and Ris hydrogen atom or -SO H group, provided at least one of the R s is SOH group.

Example 1 To 90 ml. of ethylene chloride containing 481 mmols ofe-caprolactim-O-sulfonic acid, ml. of ethylene chloride containing 3.5g. of acetoxime (48 mmols) was added dropwise with stirring, attemperatures not higher than 0 C. After the addition the mixture wasstirred for 45 minutes at room temperature, and again cooled to 0 C. orbelow. To the mixture then 50 ml. of ethylene chloride solutioncontaining 3.3 g. (48 mmols) of imidazole was added dropwise.Simultaneously with the addition, color less precipitate was formed.After the addition of imidazole, the stirring was continued for furtherminutes under cooling. The precipitate was collected by filtration. Theyield was 8.9 g. (84%). The melting point of the precipitate was l02-l05C., and its elementary analysis values were as follows: N: 18.84%, andS: 14.37%, which Well corresponded to the theoretical values ofimidazole salt of acetoxime-O-sulfonic acid (C H N O S), which are N:18.99%, and S: 14.49%.

The filtrate was concentrated under reduced pressure, and from theresulting syrup-like concentrate, 5.3 g. of ecaprolactam was recoveredby benzene extraction. The yield was 98%.

Example 2 s-caprolactim-O-sulfonic acid (48 mmols) and 6.5 g. ofacetophenone oxime (48 mmols) were allowed to react similarly toExample 1. Then 3.3 g. (48 mmols) of imidazole was added to the reactionmixture. The reaction mixture was concentrated under reduced pressure.The concentrate was dissolved in 10 ml. of ethyl alcohol, and

to the solution ethyl ether was added to form colorless precipitate. Theprecipitate was collected by filtration. The yield was 6.8 g. (50% Themelting point of the product was 92-95 C., and its elementary analysisvalues were as follows: N: 14.86% and S: 11.08%, which well correspondedto the theoretical values of imidazole salt of acetophenoneoxime-Osulfonic acid (C H N O S)which are N: 14.87% and S: 11.32%.

After distilling 01f the solvent from the filtrate by reduced pressureconcentration, 3.6 g. of e-caprolactam was recovered from theconcentrate by ethyl ether extraction. The yield was 66%.

Example 3 Seventy (70) ml. of ethylene chloride containing 48 mmols ofe-caprolactim-O-sulfonic acid was cooled to 0 C., and to which 40 ml. ofethylene chloride containing 4.7 g. (48 mmols) of cyclopentanone oximewas added dropwise with stirring. Thereafter the mixture was slowlyheated to room temperature, and then stirred for an hour. The reactionmixture was again cooled to 10 C. or below, and to which a solution of3.3 g. (48 mmols) of imidazole in 40 ml. of ethylene chloride was addeddropwise with stirring. Simultaneously with the addition, generation ofheat was observed, and colorless precipitate began to form. Theprecipitate was collected by filtration. The yield was 7.45 g. (63%).The precipitate had a melting point of 79-84" C., and elementaryanalysis values of N: 16.90% and S: 12.13%. The values well correspondedto the theoretical values of imidazole salt of cyclopentanoneoxime-O-sulfonic acid as C H N O S, which are N: 16.99% and S: 12.97%.

The filtrate was concentrated under reduced pressure, and from theconcentrate 5.2 g. of e-caprolactam was recovered by ethyl etherextraction. The yield was 96%.

Example 4 Example 3 was repeated except that the cyclopentanone oximewas replaced by cyclohexanone oxime. Thus 10.0 g; of precipitate wascollected. The yield was 80%. The precipitate had a melting point of114-ll6 C., and elementary analysis values of N: 16.18%, C: 41.54%, andH: 5.78%. The values well corresponded to the theoretical values ofimidazole salt of cyclohexanone oxime-O-sulfonic acid as C H N O S,which are N: 16.08%, C: 41.37%, and H: 5.79%.

The filtrate was concentrated under reduced pressure, and from theconcentrate 5.1 g. of e-caprolactam was obtained by ethyl etherextraction. The yield was 94%.

Example 5 Seventy (70) ml. ethylene chloride solution containing 48mmols of e-caprolactim-O-sulfonic acid was cooled to -4 C., and to whicha suspension of 9.5 g. (48 mmols) of cyclododecanone oxime in 40 ml. ofethylene chloride was added with stirring. The temperature rose to 30 C.due to the exothermic reaction. The reaction mixture was stirred for 2hours at room temperature, and cooled to 0 C. T o the mixture then 40ml. of ethylene chloride solution containing 3.3 g. (40 mmols) ofimidazole was added dropwise. Immediately colorless precipitate began toform, which was collected by filtration. The yield was 11.2 g. (68%).The precipitate had a melting point of 157l59 C., and elementaryanalysis values of N: 12.56% and S: 9.67%. The values well correspondedto the theoretical values of imidazole salt of cyclododecanone oxime-Osulfonic acid as C H N O S, which are N: 12.16% and S: 9.28%.

The filtrate was treated with activated carbon, and concentrated underreduced pressure. To the light yellow concentrate, 30 ml. of water wasadded to cause precipitation of cyclododecanone oxime. Thus 2.4 g. ofthe precipitate was collected by filtration (yield: 26% From thefiltrate, 5.2 g. of e-caprolactam was recovered by extraction withchloroform. The yield was 96%.

9 Example 6 To a solution of -methyl-e-caprolactim-O-sulfonic acid (48mmols) in 100 ml. of ethylene chloride, 40 ml. of ethylene chloridesolution containing 5.4 g. of cyclohexanone oxime (48 mmols) was addeddropwise at 10 C. with stirring. Thereafter the external cooling wasstopped, and the reaction mixture was stirred at room temperature.Within approximately 2 hours, the temperature of reaction mixturereached room temperature. The mixture was again cooled to 5 C., then 30ml. of chloroform solution containing 3.3 g. (48 mmols) of imidazole wasadded dropwise, and the mixture was stirred for 30 minutes. Then theprecipitated crystals were collected by filtration. Thus 9.77 g. ofimidazole salt of cyclohexanone oxime-O-sulfonic acid was obtained,which corresponded to 78% of the theoretical yield, i.e., 12.5 g.

The filtrate was concentrated, and the yellowish brown, glutinousresidue was homogeneously dissolved in 40 ml. of water. The solution wasextracted 5 times with each 30 ml. of chloroform, and the combinedextract was dried over anhydrous sodium sulfate, and the solvent wasremoved. Thus 7.6 g. of brown, glutinous residue was obtained. When theresidue was fractionated, 4.9 g. of 'ymethyl-e-caprolactam was obtainedas the fraction of distillate at 127130 C./6 mm. Hg. The yield was 90%.

Example 7 To 30 ml. of an ethylene chloride solution containing 24 mmolsof laurolactim-O-sulfonic acid, a solution of 2.7 g. (24 mmols) ofcyclohexanone oxime in 20 ml. of ethylene chloride was added dropwise atroom temperature with stirring. The stirring was continued for further 2hours at room temperature, after the addition had completed. Thereaction mixture was cooled to 0 C., to which a solution of 1.65 g. (24mmols) of imidazole in 20 ml. of ethylene chloride was added dropwisewith stirring. After allowing the mixture to stand overnight at roomtemperature, the precipitated 0.33 g. of crystalline imidazole sulfatewas collected by filtration.

After distilling off a major portion of the ethylene chloride from thefiltrate under reduced pressure, 4.0 g. of laurolactam (yield: 85%) wasrecovered from the residue by benzene extraction. The oily residue(benzene-insoluble component) remaining after the extraction wassuspended in 20 ml. of ethylene chloride and stirred. Thus cyclohexanoneoxime-O-sulfonic acid-imidazole salt was precipitated. The yield was 4.6g. (73%).

Example 8 T wenty-four (24) mmols of laurolactim-O-sulfonic acid and4.75 g. (24 mmols) of cyclododecanone oxime were treated similarly toExample 5, and 1.65 g. (24 mmols) of imidazole was added to the reactionmixture.

Thus precipitated cyclododecanone oxime-O-sulfonic acid-imidazole saltwas collected by filtration. The yield was 3.1 g.

The solvent was completely distilled off from the filtrate under reducedpressure, and from the resulting oily residue, 4.4 g. of laurolactam(yield: 93%) was recovered by hot benzene extraction followed byrecrystallization from water-methyl alcohol.

The yellow, oily residue remaining after the benzene extraction wasdissolved in methyl alcohol, and ethyl ether was added to the solution.Thus precipitated cyclododecanone oxime-O-sulfonic acid-imidazole saltwas collected by filtration. The yield was 8.2 g.

The cyclododecanone oxime-O-sulfonic acid-imidazole salt was dissolvedin methyl alcohol, and re-precipitated with ethyl ether forpurification. The yield was 5.8 g. (70% 10 Example 9 A suspension of 24mmols of cyclohexanone oxime-O- sulfonic acid in 50 ml. of ethylenechloride was cooled to 0 C., and into which 15 ml. of diethyl ethercontaining 1.6 g. (27 mmols) of cyclohexylamine was added dropwise withstirring. Simultaneously with the addition, the temperature of themixture rose by approximately 10 C. due to the exothermic reaction. Thesuspended cyclohexanone oxime-O-sulfonic acid was once dissolved to forma homogeneous solution, and newly colorless pre cipitate began to form.After the addition, the reaction mixture was gradually warmed up to roomtemperature, with continuous stirring. After an hours stirring at roomtemperature, the mixture was concentrated under reduced pressure at 40C. or below, until the total quantity thereof was reduced toapproximately 20 ml. To the residue 50 ml. of diethyl ether was added,and the formed precipitate was collected by filtration. The yield was6.7 g. The precipitate was washed with diethyl ether, dissolved inmethyl alcohol, re-precipitated with diethyl ether, and collected byfiltration and dried.

Thus purified precipitate had elementary analysis values as follows: N:9.29%, and S: 10.70%. The melting point was 156-158 C. The values wellcorresponded to the theoretical values of cyclohexylamine salt ofcyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 9.58%,and S: 10.96%. The yield was Example 10 Twenty-four (24) mmols ofcyclohexanone oxime-O- sulfonic acid and 1.8 g. (25 mmols) ofdiethylamine were allowed to react and treated similarly to Example 9,and 5.9 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.79%, S:12.03%, C: 45.20%, and H: 8.05%, and the melting point was 136-138 C.The values well corresponded to the caculated values of diethylaminesalt of cyclohexanone oxime O sulfonic acid as C H N O S, which are: N:10.52%, S: 12.04%, C: 45.09%, and H: 8.33 The yield was 92%.

Example 11 A suspension of cyclohexanone oxime-O-sulfonic acid (24mmols) in 50 ml. of ethylene chloride was cooled to 0 C., to which 15ml. of ethylene chloride containing 2.5 g: (25 mmols) of triethylaminewas added dropwise with stirring. Simultaneously with the addition, thesuspended solid was progressively dissolved. After the addition, thereaction mixture was stirred for an hour at room temperature, and thusformed solution was concentrated under reduced pressure to approximately20 ml. When 50 ml. of diethyl ether was added to the concentrate,colorless precipitate was formed, which was strongly hydroscopic. Theyield was 6.15 g. The elementary analysis values of the precipitate wereas follows: N: 9.13%, and S: 11.52%. The melting point could not bedetermined. The analysis values well corresponded to the theoreticalvalues of triethylamine salt of cyclohexanone oxime-O- sulfonic acid asC H N O S, which are N: 9.51% and S: 10.89%. The yield was 87%.

Example 12 Twenty-four (24) mmols of cyclohexanone oxime-O sulfonic acidand 2.0 g. (27 mmols) of tertiary butylamine were treated similarly toExample 9, and 6.32 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.14% and S:11.91%; and its melting point was 163 C. The values well corresponds tothe theoretical values of tertiary butylamine salt of cyclohexanoneoxime-O-sulfonic acid as C H N O S, which are 'N: 10.52% and S: 12.04%.The yield was 99%.

1 1 Example 13 Twenty-four (24) mmols of cyclohexanone oxime-O- sulfonicacid and 1.6 g. (27 mmols) of isopropylamine were treated similarly toExample 11, and 5.72 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 11.26% and S:12.98%, and its melting point was 107-1 10 C. The values wellcorresponded to the theoretical values of isopropylamine salt ofcyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 11.10%,and S: 12.71%. The yield was 94%.

Example 14 Twenty-four (24) mmols of cyclohexanone oxime-O- sulfonicacid and 1.6 g. (27 mmols) of n-propylamine were treated similarly toExample 11, and 5.82 g. of precipitate was obtained.

The elementary analysis values of the precipitate were: N: 10.45%, S:12.90%, C: 42.87%, and H: 7.84%. The melting point was 125-128 C. Thevalues well corresponded to the theoretical values of n-propylamine saltof cyclohexanone oxime-O-sulfonic acid as C H N O,S, which are N:11.10%, S: 12.71%, C: 42.84%, and H: 7.99%. The yield was 96% Example 15A suspension of cyclohexanone oxime-O-sulfonic acid (120 mmols) in 100ml. of ethylene chloride was cooled to C., to which 11.5 g. (130 mmols)of aniline was added dropwise with stirring. The temperature of themixture rose to 10 C. due to the exothermic reaction. After 30 minutesstirring, the formed precipitate was collected by filtration, and washedwith diethyl ether. The yield was 31.5 g.

The elementary analysis values of the precipitate were as follows: N:10.01%, C: 50.19%, and H: 6.58%. The melting point was 170-175 C. Thevalues well corresponded to the theoretical values of aniline salt of'cyclohexanone oxime-O-sulfonic acid as C H N O S, which are N: 9.78%,C: 50.33%, and H: 6.34%. The yield was 92%.

Example 16 To a solution of e-caprolactam-O-sulfonic acid (48 mmols) in100 ml. of ethylene chloride, a solution of 5.4 g. (48 mmols) ofcyclohexanone oxime in 30 ml. of eth ylene chloride was added dropwiseat -0 C., with stirring. After the addition the mixture was allowed togradualy warm up to 18 C., and cooled again to -20 C. Then ml. ofethylene chloride containing 6.24 g. (24 mmols) of stannic chloride wasadded dropwise to the mixture at said temperature. When the temperatureof the reaction mixture was slowly raised, at approximately 10 C.crystalline precipitate began to form. The temperature was furtherraised to room temperature, and thereafter the mixture was heated to 45C. for minutes. After adding 10 m. of water to the mixture undercooling, ethylene chloride was distilled off under reduced pressure.Further 40 ml. of water was added to the residue to form a solution. Thesolution was neutralized with aqueous ammonia under cooling. Thegelatinous product was removed by filtration and washed with acetone.The washing and the mother liquor were combined and concentrated todistil off the acetone. The residue was dissolved in 30 ml. of water,and the formed solution was extracted 5 times with each 30 ml. ofchloroform. The extract was dried over anhydrous sodium sulfate, and thesolvent was removed. Thus 10.0 g. of e-caprolactam was obtained. Thisresult indicates that under the specified reaction conditions, the addedcyclohexanone oxime was nearly quantitatively rearranged to caprolactam.

12 Example 17 To a solution of e-caprolactim-O sulfonic asid (48 mmols)in 70 ml. of ethylene chloride, 30 ml. of ethylene chloride containing5.42 g. (48 mmols) of cyclohexanone oxime was added dropwise at 5 C. orbelow, with stirring. After the addition, the temperature of the mixturerose gradually, and when it reached 18 C., the mixture was again cooled.At 5 C. or below, 10 ml. of ethylene chloride containing 6.25 g. (24mmols) of stannic chloride was added dropwise to the mixture. Thereafterthe external cooling was stopped, and the mixture was allowed to slowlywarm up in the atmosphere of room temperature. The temperature of thereaction mixture reached room temperature after an hour, and furtherrose due to the exothermic reaction, to as high as 30.0 C. Thetemperatures above room temperature continued for 2 hours. In themeantime, crystalline precipitate was gradually formed. After 15 hoursfrom the time when the reaction mixture regained room temperature, theprecipitate was collected by filtration. Thus 6.10 g. ofe-caprolactam-stannic chloride complex was obtained. The yield was 52%.

The filtrate was concentrated, and the residue was dissolved in 40 ml.of water. The solution was neutralized with aqueous ammonia undercooling. The gelatinous product was removed by filtration and washedwith acetone. The washing was combined with the former filtrate, andacetone was distilled off therefrom by concentration. The aqueoussolution formed by dissolving the residue in 30 ml. of water wasextracted 5 times with each 30 ml. of chloroform. The extract was driedover anhydrous sodium sulfate and the solvent was removed. Thus 6.2 g.of e-caprolactam was obtained. The total yield of ecaprolactam was 83%.

Example 18 To a solution of e-caprolactam-O-sulfonic acid (48 mmols) in70 ml. of ethylene chloride, 30 ml. of ethylene chloride containing 5.42g. (48 mmols) of cyclohexanone oxirne was added dropwise at 5 C. orbelow with stirring. Then 10 ml. of ethylene chloride containing 6.25 g.(24 mmols) of stannic chloride was added dropwise. After the additionthe external cooling was stopped, and the reaction mixture was left atroom temperature. After an hour the temperature of the reaction mixturereached room temperature, and further rose, due to the exothermicreaction, to 30 C. at the highest. The reaction mixture was stirred for3 hours at room temperature, and cooled again to S C. or below.Whereupon 30 ml. of ethylene chloride solution containing 5.42 g. (48mmols) of cyclohexanone oxime, and then 10 ml. of ethylene chloridesolution containing 6.25 g. (24 mmols) of stannic chloride, were addeddropwise to the reaction mixture by the order stated. Then the externalcooling was stopped. The temperature of the reaction mixture slowlyrose, when it was left at room temperature, to room temperature after 2hours. The temperature further rose due to the exothermic reaction, toreach 27.5 C. finally. The mixture was allowed to stand for 20 hours atroom temperature, and the formed precipitate was collected byfiltration. Thus 16.97 g. of e-caprolactam-stannic chloride complex wasobtained. The yield was 73%.

The mother liquor separated from the precipitate was concentrated, andthe residue was dissolved in water and neutralized with aqueous ammoniaunder cooling. The gelatinous product was removed by filtration, andwashed with acetone. The washing and mother liquor were combined andconcentrated. The residue was dissolved in 30 ml. of water, and thesolution was extracted 5 times with each 30 ml. of chloroform. Theextract was dried over anhydrous sodium sulfate. Recovering thechloroform by distillation, 6.6 g. of e-caprolactam was obtained. Thetotal yield of e-caprolactam was 89%.

13- Example 19 To a solution of .e-caprolactim-O-sulfonic acid (48mmols) in 80 ml. of ethylene chloride, 30 ml. of ethylene chloridecontaining 5.4 g. (48 mmols) of cyclohexanone oxime was added dropwiseat 12-4.5 C. with stirring. The resulting solution was first heated toC., cooled again to 10" C., and to which 25 ml. of ethylene chloridecontaining 7.17 g. (24 mmols) of antimony pentachloride was addeddropwise. The addition completed within minutes. The temperature of themixture then was -4 C. The external cooling was stopped, and the mixturewas stirred at room temperature. The temperature of the mixture reachedroom temperature within an hour. The stirring was further continued foradditional 3 hours, and then the reaction mixture was neutralized withaqueous ammonia under cooling. Thus formed precipitate was removed byfiltration, and washed with water. The filtrate and the washing werecombined, and extracted 5 times with each 50 ml. of chloroform.

The extract was dried over anhydrous sodium sulfate, and chloroform wasremoved. Thus 9.1 g. of e-caprolactam was obtained, which correspondedto 84% of the theoretical .e-caprolactam yield, i.e., 10.8 g., under theassumption that the added cyclohexanone oxime were completelyrearranged.

Example To a solution of ecaprolactim-O-sulfonic acid (48 mmols) in 70m1. of ethylene chloride, 20 ml. of ethylene chloride containing 5.4 g.(48 mmols) of cyclohexanone oxime was added dropwise at 11 C. to 5" C.with stirring. To the mixture then 20 ml. of ethylene chloridecontaining 6.92 g. of boron trifluoride-ethyl ether complex was addeddropwise at 10 C. The addition completed 7 minutes. The temperature ofthe reaction mixture then was 7 C. The external cooling was stopped, andthe mixture was continuously stirred at room temperature. Thetemperature of the mixture reached room temperature after 40 minutes.After additional 4 hours stirring at room temperature, ml. of water wasadded to the mixture. Distilling ethylene chloride off from the mixtureunder reduced pressure the aqueous phase was extracted 5 times with each50 ml. of chloroform. The extract was dried over anhydrous sodiumsulfate, and from which the solvent was recovered. Thus 9.9 g. ofe-caprolactam containing cyclohexanone and oxime thereof was obtained.The e-caprolactam content was 7.15 g., which corresponded to 66% of thetheoretical e-caprolactam yield, i.e., 10.8 g., under the assumptionthat all the cyclohexanone oxime added were rearranged.

Examples 21-3 6 In these Examples, lactim-O-sulfonic acids were allowedto react with alcohols by one of the following four methods, and theformed lactams and alcohol-O-sulfonic acids were separately recovered.

[Method A] To 80 ml. of ethylene chloride containing 48 mmols oflactim-O-sulfonic acid, 10 ml. of ethylene chloride containing 48 mmolsof alcohol was added dropwise with stirring at room temperature. Themixture was then stirred at room temperature for 30 minutes, heated to50 C., and further stirred for 30 minutes at 50 C. The reaction mixturewas concentrated under reduced pressure, to allow recovery of theethylene chloride.

The syrup-like concentrate was dissolved in 50 ml. of ice water, and thesolution was neutralized with lON aqueous caustic soda. The solution wasthen extracted 5 times with each 20 ml. of chloroform. The extract wasdried over anhydrous sodium sulfate, from which chloroform was expelledto leave free lactam.

The aqueous solution remaining after chloroform extraction wasconcentrated under reduced pressure, and

14 20 ml. of ethyl alcohol was added to the concentrate. Allowing themixture to stand, precipitated crystalline sodium alcohol-O-sulfonatewas collected by filtration.

[Method B] To ml. of ethylene chloride containing 48 mmols oflactirn-O-sulfonic acid, 10 ml. of ethylene chloride containing 48 mmolsof alcohol was added dropwise at room temperature vw'th stirring. Themixture was thereafter stirred for an hour at room temperature, heatedto 50 C., and further stirred for an hour at 50 C. The reaction mixturewas concentrated under reduced pressure to allow recovery of ethylenechloride.

The syrup-like concentrate was dissolved in 30 ml. of water, andneutralized with sodium bicarbonate. The aqueous solution was thenextracted 5 times with each 20 ml. of chloroform, and the extract wasdried over anhydrous sodium sulfate. Thus removing chloroform therefrom,lactam was obtained.

The aqueous solution remaining after the chloroform extraction wastreated with activated carbon. Then 100 ml. of an aqueous solutioncontaining 48 mmols of S-benzylthioformamidine hydrochloride was addedto the aqueous solution. In case no precipitate was formed in the aboveprocedure, the resultant solution was further concentrated under reducedpressure and ethyl alcohol was added to the concentrate. Thus formedcrystalline precipitate of alcohol-O-sulfonic acidS-benzylthioformamidine salt was collected by filtration.

[Method C] To 80 ml. of ethylene chloride containing 48 mmols oflactim-O-sulfonic acid, 20 ml. of ethylene chloride containing 24 mmolsof alcohol was added dropwise at room temperature with stirring.Thereafter the mixture was stirred for 30 minutes at room temperature,heated to 50 C., and further stirred for 30 minutes at 50 C. Thereaction mixture was concentrated under reduced pressure, to allowrecovery of ethylene chloride.

The syrup-like concentrate was dissolved in 20 ml. of water, andneutralized with aqueous barium hydroxide. The aqueous solution wasextracted 5 times with each 20 ml. of chloroform. The extract was driedover anhydrous sodium sulfate, and chloroform was expelled therefrom toleave free lactam.

The aqueous solution remaining after the chloroform extraction wastreated with activated carbon, and concentrated under reduced pressureto approximately 5 ml. Ethyl alcohol was added to the concentrate tocause precipitation of barium alcohol-0,0-disulfonate dihydrate, whichwas collected by filtration.

[Method D] To ml. of ethylene chloride containing 48 mmols oflactim-O-sulfonic acid, 20 ml. of ethylene chloride containing 48 mmolsof alcohol was added dropwise at 10 C. or below with stirring. Then themixture was allowed to stand for 12 hours at room temperature. Thereaction mixture was concentrated under reduced pressure to allowrecovery of ethylene chloride.

Upon addition of 50 ml. of water to the syrup-like concentrate, lactamwas precipitated. The aqueous solution was neutralized with sodiumbicarbonate, and the lactam was collected by filtration.

The filtrate was concentrated under reduced pressure, and to theconcentrate ethyl alcohol was added to cause precipitation of sodiumalcohol-O-sulfonate monohydrate, which was collected by filtration.

The results of Examples 21 through 36 are collectively given in thefollowing table, in which BTFA stands for S-benzylthioformamidine,

rose gradually to 13 C. Then again the mixture was cooled to 30 C., towhich imidazole (3.3 g., 48 mmols) was added with stirring. Immediatelycolorless crystals were precipitated. After two hours stirring at roomtemperature, 6.0 g. of the colorless crystals were collected byfiltration, which was identified with thiophenol-S-sulfonicacid-imidazole salt (m.p. 1015-1035 C.) synthesized by known method, byIR spectrum. The mother liquor from which the crystals had been filteredoff was concentrated under reduced pressure to allow distillation off ofethylene chloride. The residue was dissolved in 30 ml. of water, andneutralized with aqueous ammonia. The aqueous solution was extractedwith benzene (30 ml. 2). The aqueous phase separated from the benzenephase was extracted with chloroform (40 ml. From the chloroform extract,4.95 g. (91%) of e-caprolactam was obtained.

Example 39 To a solution of e-caprolactim-O-sulfonic acid (48 mmols) inethylene chloride (70 ml.), another solution of cyclohexylarnine (9.5g., 96 mmols) in ethylene chloride (30 ml.) was added dropwise at roomtemperature, with stirring. The addition required minutes, and at theend thereof the temperature of the reaction mixture reached 37 C. Themixture was further stirred for 5 hours at room temperature, andfiltered. Thus 3.67 g. of colorless crystals were collected, which wasconfirmed to be N- cyclohexylsulfamic acid cyclohexylammonium saltcontaining a minor amount of cyclohexylamine sulfate, by means ofinfrared absorption spectrum. The crystals were treated with 30 ml. ofwater, and whereupon 0.63 g. of pure N-cyclohexylsulfamic acidcyclohexylammonium salt was obtained.

The ethylene chloride solution separated from the above crystallinemixture by filtration was concentrated under reduced pressure. Theresidue was dissolved in water, and the aqueous solution was renderedacidic with 1N hydrochloric acid, and extracted 4 times with each each50 ml. of chloroform. All the extracts were combined, and from whichchloroform was removed. The residue was again dissolved in water, andmade basic with 1N caustic soda. The aqueous solution was extracted 5times with each 50 ml. of chloroform. The extract was dried overanhydrous sodium sulfate and the solvent was removed. Thus 4.1 g. (76%)of e-caprolactam was obtained.

Example 40 To a solution of e-caprolactim-O-sulfonic acid (48 mmols) inethylene chloride (80 ml.), another solution of benzylamine (10.3 g., 96mmols) in ethylene chloride ml.) was added dropwise at room temperaturewith stirring. The addition required 20 minutes. In the meantime, thetemperature of the reaction mixture reached at the highest 40 C., andcrystals were precipitated. The reaction mixture was heated under refluxfor 3 hours and cooled. The crystalline precipitate was collected byfiltration. Thus 7.2 g. of N-benzylsulfamic acid benzylammonium salt wasobtained, which was identified with the named salt as its infraredabsorption spectrum was iden tical with that of the named compoundsynthesized by known means. The yield was 51%. The mother liquorseparated from the sulfamic acid salt by filtration was concentratedunder reduced pressure, and the residue was dissolved in water. Theaqueous solution was rendered acidic with 0.1 N hydrochloric acid, andextracted 5 times with each 50 ml. of chloroform. The extract was driedover anhydrous sodium sulfate, and chloroform was recovered therefrom.Thus 2.9 g. (54%) of e-caprolactam was obtained.

Example 41 To a solution of e-caprolactim-o-sulfonic acid (48 mmols) inethylene chloride (80 ml.), another solution of aniline (8.93 g., 96mmols) in ethylene chloride (20 ml.) was added dropwise at --5 C. orbelow with stirring. After the addition the stirring was continued for30 minutes, and thereafter the reaction mixture was heated under refluxfor an hour. The mixture was allowed to stand in the atmosphere of roomtemperature and to cool off, and the precipitated crystals werecollected by filtration. Thus 11.1 g. of phenylsulfamic acid aniliniumsalt was obtained. The yield was 87%.

The mother liquor separated from the crystals was concentrated underreduced pressure. Then the aqueous solution formed by adding 50 ml. ofwater to the residue was extracted with 50 m1. of diethyl ether. Theaqueous phase separated from the ether phase was extracted 5 times witheach 50 ml. of chloroform. From the chloroform extract, 5.0 g., ofe-caprolactam was obtained. The yield of the e-caprolactam was 93% Whatis claimed is:

1. A process for the preparation of lactams and sulfonic acidderivatives of active hydrogen-containing organic compounds whichcomprises reacting at a temperature of 30 to 50 C. a lactim-O-sulfonicacid of the formula C-OSOaH l 2)n N wherein n is a number of 3 to 11,and R and R are each a hydrogen atom, an alkyl group of up to 4 carbonatoms or alkenyl group of 2 to 4 carbon atoms, with an activehydrogen-containing compound selected from the group consisting of (i)alicyclic ketoximes of the formula wherein 11, R and R are as definedabove; (ii) acyclic ketoximes of the formula wherein R and R are each analkyl group of up to 10 carbon atoms, cycloalkyl group of 3 to 12 carbonatoms, aryl group of 6 to 14 carbon atoms, or aralkyl group of 7 to 14carbon atoms; (iii) monohydric alcohols of the formula wherein R is analkyl group of up to 18 carbon atoms, cycloalkyl group of 4 to 12 carbonatoms, or aralkyl group of 7 to 14 carbon atoms;

(iv) glycols of the formula wherein R is an alkylene group of 2 to 8carbon atoms, or xylylene group, and m is zero or an integer of 1 to 3;

(v) polyhydric alcohols selected from the group consisting of glycerine,1,2,6-hexanetriol, 1,1,1- trihydroxymethylpropane, pentaerythritol andpolyvinyl alcohol;

(vi) phenols of the formulae and (R1)k wherein R is a hydroxyl group, analkyl group of up to 4 carbon atoms or nitro group, and k is 0, 1, or 2;

(vii) thiols of the formula wherein R is an alkyl group of up to carbonatoms, cycloalkyl group of 4 to 12 carbon atoms, aralkyl group of 7 to14 carbon atoms, or an aryl group of 6 to 14 carbon atoms; and

(viii) primary and secondary amines of the formula,

under substantially anhydrous conditions.

2. A process for the preparation of lactams and ketoxime-O-sulfonicacids, which comprises reacting a lactim- O-sulfonic acid of the formulawherein n is a number of 3 to 11, and R and R are each a hydrogen atom,an alkyl group of up to 4 carbon atoms or alkenyl group of 2 to 4 carbonatoms, with a ketoxime selected from the group consisting of (i)alicyclic ketoximes of the formula wherein in, R and R are as definedabove; and (ii) acyclic ketoximes of the formula NOH wherein R and R areeach on alkyl group of up to 10 carbon atoms, cycloalkyl group of 3 to12 carbon atoms, aryl group of 6 to 14 carbon atoms, or aralkyl group of7 to 14 carbon atoms,

under substantially anhydrous conditions and in an inert organicsolvent, at a temperature within the range of from 30 C. to 50 (3.;adding to the resulting reaction mixture an organic base selected fromthe group consisting of aliphatic amines, alicyclic amines, aromaticamines, nitrogen-containing heterocyclic compounds and amidines;recovering the ketoxime-O-sulfonic acid in the form of a salt of saidorganic base, as a solid; and recovering said lactam from the formedmother liquor.

3. A process for the preparation of lactams, which comprises reacting alactim-O-sulfonic acid of the formula COSOaH Rim). ll N wherein n is anumber of 3 to 11, and R and R are each a hydrogen atom, an alkyl groupof up to 4 carbon atoms or alkenyl group of 2 to 4 carbon atoms, with analicyclic ketoxime of the formula wherein 12, R and R are as definedabove, under substantially anhydrous conditions, in an inert organicsolvent, at a temperature within the range of from 30 C. to C.; andsubsequent to the reaction adding to the reaction system a halide of theformula MX wherein M is an element of Group B, HB, IIA, IVA,

IVB, VA, or VIII of the Periodic Table, X is a halogen atom, and p is anumber equal to the valency of M,

thereby converting the formed lactam to a complex with said halide whilerearranging the formed alicyclic ketoxime-O-sulfonic acid to alactim-O-sulfonic acid.

References Cited UNITED STATES PATENTS 3,119,814 1/1964 Bigot et al260239.3 A 3,687,938 8/1972 Masaki et al 260239.3 A

HENRY R. JILES, Primary Examiner R. T. BOND, Assistant Examiner US. Cl.X.R.

260-2393 R, 326.82, 326.5 FN, 326.5 FL, 293.86, 566 A, 553 R, 513.6,451, 456, 239 B, 293.85

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.,836,525 Dated September 17, 1974 Inventor-(s) Mitsuo MASAKI ET AL It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Heading, insert 'patentees' Foreign Application Data as follows:

-- Japanese Application No. 44 7399O/69, filed Sept. 19, 1969 JapaneseApplication No. 44-73991/69, fjiled Sept. 19, 1969 In Claim 1, lastformula inv column 18': cancel "R -OH" and substitute therefor RS-SHSigned and sealed this 3rd day of. December 1974.

(SEAL) Attest: I

M. GIBSGN JR. C. MARSl IALL DANN ggiting Officer Commissioner of PatentsF ORM PO-l 050 (10-69) USCOMM-DC 60376-969 v 11.5. GOVERNMENT Pmm'mcOFFICE: @959 o-ass-n-a

